2-acetyl-3ξ-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-acrylic acid ethyl ester | 81132-43-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 2-acetyl-3ξ-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-acrylic acid ethyl ester
• 英文别名: 2-acetyl-3ξ-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-acrylic acid ethyl ester；2-Acetyl-3ξ-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-acrylsaeure-aethylester
• CAS: 81132-43-6
• 化学式: C₁₂H₁₈O₅
• 分子量: 242.272
• InChiKey: HOSHBVVKMRGFDA-VIFPVBQESA-N

物化性质

• 沸点：
  332.2±32.0 °C(Predicted)
• 密度：
  1.145±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.22
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2-acetyl-3ξ-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-acrylic acid ethyl ester 、 丙二腈 在 哌啶 作用下， 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Michael addition of malononitrile to chiral α-acylacrylates

  摘要：

  Starting from 2,3-0-isopropylidene-D-glyceraldehyde (1), 3-O-methyl and 3-O-benzyl-1,2-O-isopropylidene-alpha-D-xylo-pentodialdo-1,4-furanose (4a, 4b), we describe the synthesis of the alpha-acyl-beta-alkyl substituted acrylates 2 and 5. The Michael addition of malononitrile to these substrates gives the polyfunctionalized 2-amino-4H-pyrans 3 and 6 with moderate diastereoselectivity and reasonable overall yield from diols 7 and 8a,b. A detailed analysis is performed scanning different type of bases in the Michael reaction. We find that, while for acceptor 2 no changes are observed, for compound 5 the stereochemical outcome of the 1,4-addition is reversed in going from piperidine, sodium hydride or potassium t-butoxide to lithium diisopropylamide or lithium diisopropylamide/magnesium iodide reagent. Several models for rationalising the results are proposed.

  DOI：

  10.1016/s0040-4020(01)87984-9
• 作为产物：
  描述：

  双丙酮-D-甘露糖醇 在 哌啶 sodium periodate 作用下， 以 甲醇 、 水 、 甲苯 为溶剂， 反应 3.5h， 生成 2-acetyl-3ξ-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-acrylic acid ethyl ester
  参考文献：
  名称：

  Michael addition of malononitrile to chiral α-acylacrylates

  摘要：

  Starting from 2,3-0-isopropylidene-D-glyceraldehyde (1), 3-O-methyl and 3-O-benzyl-1,2-O-isopropylidene-alpha-D-xylo-pentodialdo-1,4-furanose (4a, 4b), we describe the synthesis of the alpha-acyl-beta-alkyl substituted acrylates 2 and 5. The Michael addition of malononitrile to these substrates gives the polyfunctionalized 2-amino-4H-pyrans 3 and 6 with moderate diastereoselectivity and reasonable overall yield from diols 7 and 8a,b. A detailed analysis is performed scanning different type of bases in the Michael reaction. We find that, while for acceptor 2 no changes are observed, for compound 5 the stereochemical outcome of the 1,4-addition is reversed in going from piperidine, sodium hydride or potassium t-butoxide to lithium diisopropylamide or lithium diisopropylamide/magnesium iodide reagent. Several models for rationalising the results are proposed.

  DOI：

  10.1016/s0040-4020(01)87984-9

文献信息

• Lopez Aparicio et al., Anales de la Real Sociedad Espanola de Fisica y Quimica, 1958, vol. <B> 54, p. 705,712
  作者：Lopez Aparicio et al.

  DOI：——

  日期：——
• Alonso Cermeno et al., 1972, vol. 68, p. 285,289
  作者：Alonso Cermeno et al.

  DOI：——

  日期：——
• The first asymmetric synthesis of polyfunctionalized 4H-pyrans via Michael addition of malononitrile to 2-acyl acrylates
  作者：Rafael González、Nazario Martín、Carlos Seoane、JoséL Marco、Armando Albert、Félix H Cano

  DOI：10.1016/0040-4039(92)80031-e

  日期：1992.6

  Starting from (R)-2,3-O-isopropylideneglyceraldehyde, the first asymmetric synthesis of 4H-pyrans (4BAR) has been developed; a de tailed X-ray structural and stereochemical study has established as R the absolute configuration at the new stereocenter in compounds 4.